微/纳米结构复合型TiO_2光催化剂的制备及其光催化性能研究
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摘要
半导体TiO_2光催化剂在空气净化、污水处理、自洁净玻璃、防雾和抗菌等领域具有广阔的应用前景。目前,TiO_2光催化剂还存在光催化活性较低以及对太阳光的利用率很低等难题。近年来,TiO_2光催化剂的改性技术得到了迅速发展,包括半导体复合、过渡金属离子掺杂、非金属掺杂、贵金属沉积、表面光敏化等方法。
本论文针对纳米TiO_2的缺点,重点研究纳米TiO_2与其它半导体的复合,利用表面吸附层反应成功地将纳米TiO_2与ZnO和CuO复合,制备了微/纳米结构的ZnO/TiO_2和CuO/TiO_2复合物,并对其光催化活性进行了研究。主要内容如下:
第一,综述了半导体光催化剂TiO_2的光催化反应机理,以及TiO_2光催化剂的研究进展及其应用。
第二,为了使得光生电子和光生空穴的寿命延长,提高TiO_2的光催化活性,将其与禁带宽度相近的ZnO复合。以Zn(Ac)2和NaOH为原料,采用湿法合成微米尺寸的花状和棒状的ZnO微晶,将其作为纳米TiO_2的载体,利用表面吸附层反应成功地制备了微/纳米结构的ZnO/TiO_2复合物。
第三,为了拓宽TiO_2光催化剂的光响应范围,并且能更好的分离e~--h~+对,提高光催化量子产率,将其与禁带宽度较窄的CuO复合。以CuSO_4·5H_2O、NaOH和C_6H_(12)O_6为原料,在常压下70℃时,不加任何添加剂的情况下,制备微米尺寸的球状和立方块状Cu_2O微晶,经热处理后得球状和立方块状CuO,将其作为纳米TiO_2的载体,利用表面吸附层反应成功地制备了微/纳米结构的CuO/TiO_2复合物。
第四,通过光催化实验,验证复合光催化剂的光催化活性。以甲基橙为模拟废水,将微/纳米结构的ZnO/TiO_2和CuO/TiO_2复合物与甲基橙溶液混合均匀,分别经高压汞灯或日光灯照射反应,研究其光催化性能。实验结果得出了花状和棒状ZnO/TiO_2复合催化剂分别是摩尔比为1:3和1:1的光催化活性最好;球状和立方块状CuO/TiO_2的复合催化剂均为复合比例为2:1的光催化性能最好。并用催化活性最好的催化剂研究不同浓度的催化剂、不同甲基橙初始浓度对光催化效果的影响。
As a semiconductor photocatalyst, considerable attention has been focused on TiO_2 owing to its unique properties and promising applications, such as air purification, waste water treatment, self-cleanness, mist prevention, bacillus resistance and so on. However, it is still a great challenge to overcome the problems of low photocatalytic activity and low utilization of sunlight. In recent years, there is a rapid development of the improvement of TiO_2 photocatalyst, including the compositing of semiconductor, the doping of the transition metal ions and the non-metallic ions, the depositing of the precious metals and the sensitizing of TiO_2 surface.
In this paper, have been focused on the combination of nanosized TiO_2 and other semiconductors materials based on its disadvantages. Micro/nano-structures ZnO/TiO_2 and CuO/TiO_2 composites photocatalyst were prepared by the hydrolyzation method in the surface adsorption layer of the micron dimentional ZnO and CuO. And the photocatalytic activity of the composites was given as a detailed research. The main contents are as follows:
Firstly, the reaction mechanisms, the research progresses and the applications of TiO_2 photocatalysts were reviewed.
Secondly, in order to keep light electron and hole prolonging and improve the photocatalytic activity, TiO_2 was composited with ZnO which has the similar band-gap. Zn(Ac)_2 and NaOH are used without further purification, the micron dimentional flower-shape and rod-shape ZnO microcrystallines were prepared through a facile wet synthesis. Additionally, the micro/nano ZnO/TiO_2 composite photocatalyst was successfully synthesized by the surface adsorption layer reaction with these microcrystallines as the carriers.
Thirdly, TiO_2 was composited with CuO which has the narrower band-gap to broaden the light response range, separate electron-hole pairs, and improve the photocatalytic activity. In a typical preparation, CuSO_4·5H_2O, NaOH, and C_6H_(12)O_6 were all commercially available and used without further purification, the micron dimentional spherical and cubic Cu2O microcrystalline were prepared at 70℃and atmospheric pressure without any surfactants. After heat treatment, the spherical and cubic CuO were obtained. Then with CuO as the carrier of nanometer TiO_2, the micro/nano CuO/TiO_2 composite was successfully prepared by the surface adsorptive layer reaction.
Fourthly, experiments were carried out to test the photocatalytic activity of the composite photocatalyst. Methyl orange was selected as a representative dye pollutant of industrial wastewaters. The photoreactor was designed with a high-pressure mercury lamp or fluorescent irradiation, and the abtained micro/nano ZnO/TiO_2 and CuO/TiO_2 was added as the photocatalyst into Methyl orange. The experimental results indicated that the flower-shape and rod-shape ZnO/TiO_2 composites showed the best photocatalytic activity with the mole ratio of ZnO:TiO_2 3 to 1 and 1 to 1. However, the spherical and cubic of CuO/TiO_2 composites gave the best light catalytic performance with the both mole ratio of CuO:TiO_2 2 to 1. The effects of different concentrations of catalysts and different initial concentrations of methyl orange on photocatalytic activity were also studied using the catalysts which had the best catalytic activity.
本论文针对纳米TiO_2的缺点,重点研究纳米TiO_2与其它半导体的复合,利用表面吸附层反应成功地将纳米TiO_2与ZnO和CuO复合,制备了微/纳米结构的ZnO/TiO_2和CuO/TiO_2复合物,并对其光催化活性进行了研究。主要内容如下:
第一,综述了半导体光催化剂TiO_2的光催化反应机理,以及TiO_2光催化剂的研究进展及其应用。
第二,为了使得光生电子和光生空穴的寿命延长,提高TiO_2的光催化活性,将其与禁带宽度相近的ZnO复合。以Zn(Ac)2和NaOH为原料,采用湿法合成微米尺寸的花状和棒状的ZnO微晶,将其作为纳米TiO_2的载体,利用表面吸附层反应成功地制备了微/纳米结构的ZnO/TiO_2复合物。
第三,为了拓宽TiO_2光催化剂的光响应范围,并且能更好的分离e~--h~+对,提高光催化量子产率,将其与禁带宽度较窄的CuO复合。以CuSO_4·5H_2O、NaOH和C_6H_(12)O_6为原料,在常压下70℃时,不加任何添加剂的情况下,制备微米尺寸的球状和立方块状Cu_2O微晶,经热处理后得球状和立方块状CuO,将其作为纳米TiO_2的载体,利用表面吸附层反应成功地制备了微/纳米结构的CuO/TiO_2复合物。
第四,通过光催化实验,验证复合光催化剂的光催化活性。以甲基橙为模拟废水,将微/纳米结构的ZnO/TiO_2和CuO/TiO_2复合物与甲基橙溶液混合均匀,分别经高压汞灯或日光灯照射反应,研究其光催化性能。实验结果得出了花状和棒状ZnO/TiO_2复合催化剂分别是摩尔比为1:3和1:1的光催化活性最好;球状和立方块状CuO/TiO_2的复合催化剂均为复合比例为2:1的光催化性能最好。并用催化活性最好的催化剂研究不同浓度的催化剂、不同甲基橙初始浓度对光催化效果的影响。
As a semiconductor photocatalyst, considerable attention has been focused on TiO_2 owing to its unique properties and promising applications, such as air purification, waste water treatment, self-cleanness, mist prevention, bacillus resistance and so on. However, it is still a great challenge to overcome the problems of low photocatalytic activity and low utilization of sunlight. In recent years, there is a rapid development of the improvement of TiO_2 photocatalyst, including the compositing of semiconductor, the doping of the transition metal ions and the non-metallic ions, the depositing of the precious metals and the sensitizing of TiO_2 surface.
In this paper, have been focused on the combination of nanosized TiO_2 and other semiconductors materials based on its disadvantages. Micro/nano-structures ZnO/TiO_2 and CuO/TiO_2 composites photocatalyst were prepared by the hydrolyzation method in the surface adsorption layer of the micron dimentional ZnO and CuO. And the photocatalytic activity of the composites was given as a detailed research. The main contents are as follows:
Firstly, the reaction mechanisms, the research progresses and the applications of TiO_2 photocatalysts were reviewed.
Secondly, in order to keep light electron and hole prolonging and improve the photocatalytic activity, TiO_2 was composited with ZnO which has the similar band-gap. Zn(Ac)_2 and NaOH are used without further purification, the micron dimentional flower-shape and rod-shape ZnO microcrystallines were prepared through a facile wet synthesis. Additionally, the micro/nano ZnO/TiO_2 composite photocatalyst was successfully synthesized by the surface adsorption layer reaction with these microcrystallines as the carriers.
Thirdly, TiO_2 was composited with CuO which has the narrower band-gap to broaden the light response range, separate electron-hole pairs, and improve the photocatalytic activity. In a typical preparation, CuSO_4·5H_2O, NaOH, and C_6H_(12)O_6 were all commercially available and used without further purification, the micron dimentional spherical and cubic Cu2O microcrystalline were prepared at 70℃and atmospheric pressure without any surfactants. After heat treatment, the spherical and cubic CuO were obtained. Then with CuO as the carrier of nanometer TiO_2, the micro/nano CuO/TiO_2 composite was successfully prepared by the surface adsorptive layer reaction.
Fourthly, experiments were carried out to test the photocatalytic activity of the composite photocatalyst. Methyl orange was selected as a representative dye pollutant of industrial wastewaters. The photoreactor was designed with a high-pressure mercury lamp or fluorescent irradiation, and the abtained micro/nano ZnO/TiO_2 and CuO/TiO_2 was added as the photocatalyst into Methyl orange. The experimental results indicated that the flower-shape and rod-shape ZnO/TiO_2 composites showed the best photocatalytic activity with the mole ratio of ZnO:TiO_2 3 to 1 and 1 to 1. However, the spherical and cubic of CuO/TiO_2 composites gave the best light catalytic performance with the both mole ratio of CuO:TiO_2 2 to 1. The effects of different concentrations of catalysts and different initial concentrations of methyl orange on photocatalytic activity were also studied using the catalysts which had the best catalytic activity.
引文
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